| AVS 65th International Symposium & Exhibition | |
| Surface Science Division | Thursday Sessions |
| Session SS+EM+PS+TF-ThA |
| Session: | Deposition, Etching and Growth at Surfaces |
| Presenter: | Borja Cirera, IMDEA Nanoscience, Spain |
| Authors: | B. Cirera, IMDEA Nanoscience, Spain J. Björk, Linköping University, Sweden G. Bottari, Universidad Autonoma Madrid, Spain T. Torres, Universidad Autonoma Madrid, Spain R. Miranda, IMDEA Nanoscience, Spain D. Ecija, IMDEA Nanoscience, Spain |
| Correspondent: | Click to Email |
Metallation of surface confined porphyrinoid architectures have emerged as an important research topic due to its importance for biological phenomena and potential applications including optoelectronics, nanomagnetism, sensing and catalysis.
Hereby, the in-situ design of mutant porphyrinoids, either by selection of unconventional metal centers like lanthanides or by choosing different backbones, is attracting great attention. In this talk we report our latest research regarding the metallation by dysprosium, an archetype lanthanide metal for magnetic applications, of porphyrinoid species of distinct cavity size.
On one hand, the deposition of Dy on top a submonolayer of fluorinated tetraphenyl porphyrin species on Au(111) affords the expression of three different Dy-derived compounds, which are identified as the: initial, intermediate and final metallated states. Importantly, the initial metallated complexes exhibit a narrow zero bias resonance at the Fermi level that is assigned to a molecular Kondo resonance with Tk ≈ 120 K, which can be switched off by means of vertical manipulation.
On the other hand, the adsorption on Au(111) of an expanded hemiporphyrazine with 27 atoms in its internal cavity is investigated, showing a long-range orientational self-assembly. Furthermore, a spatially controlled “writing” protocol on such self-assembled architecture is presented, based on the STM tip-induced deprotonation with molecular precision of the inner protons. Finally, the capability of these surface-confined macrocycles to host lanthanide elements is assessed, introducing a novel off-centered coordination motif.
The presented findings represent a milestone in the fields of porphyrinoid chemistry and surface science, revealing a great potential for novel surface patterning, opening new avenues for molecular level information storage, and boosting the emerging field of surface-confined coordination chemistry involving f-block elements.